Preparation of a high molecular weight poly(arylene sulfide ketone)

ABSTRACT

A process, and product produced therefrom, for preparing a high molecular weight poly(arylene sulfide ketone) from the reaction product of an alkali metal bisulfide with an alkali metal hydroxide, employing molar excess of alkali metal bisulfide with respect to the alkali metal hydroxide. A process, and product produced therefrom, for preparing a high molecular weight poly(arylene sulfide ketone) employing an alkali metal sulfide and an alkali metal hydrosulfide, wherein the alkali metal .[.sulfide.]. .Iadd.hydrosulfide .Iaddend.is added in a molar excess with respect to the alkali metal .[.hydrosulfide.]. .Iadd.sulfide.Iaddend..

.Iadd.This is a reissue application of Ser. No. 905,615, filed Sept. 5,1986, now U.S. Pat. No. 4,716,212, patented Dec. 29, 1987. .Iaddend.

FIELD OF THE INVENTION

This invention relates to a method for preparing poly(arylene sulfideketone)s. The invention further relates to poly(arylene sulfide ketone)sprepared from the reaction product of an alkali metal hydrosulfide withan alkali metal hydroxide. The invention further relates to poly(arylenesulfide ketone)s prepared employing an alkali metal sulfide and analkali metal hydrosulfide. The invention also relates to fibers andother articles of manufacture prepared from these poly(arylene sulfideketone)s.

BACKGROUND OF THE INVENTION

Poly(arylene sulfide ketone)s, PASK, are an important class ofengineering thermoplastics. Poly(arylene sulfide ketone)s are ofcommercial interest for fil,m fiber, moldings and composite applicationsbecause of their high melting points. One process for producingpoly(arylene sulfide ketone)s involves the reaction of adihalobenzophenone such as a dichlorobenzophenone with an alkali metalsulfide. The alkali metal sulfide is prepared by the reaction of analkali metal hydrosulfide with an alkali metal hydroxide using virtuallyprecise equimolar amounts (stoichiometric amounts) of the alkali metalhydrosulfide with respect to the alkali metal hydroxide, since an excessof either component has been considered undesirable.

However, a major disadvantage with the poly(arylene sulfide ketone)s hasbeen a relatively low molecular weight. It would be most desirable to beable to produce poly(arylene sulfide ketone)s having a relatively highmolecular weight. The high molecular weight poly(arylene sulfideketone)s would exhibit improved impact strength and toughness whencompared to low molecular weight poly(arylene sulfide ketone)s.

It is an object of my invention to provide a process for preparing ahigh molecular weight poly(arylene sulfide ketone). It is a furtherobject of my invention to prepare high molecular weight poly(arylenesulfide ketone)s.

SUMMARY OF THE INVENTION

I have discovered that relatively high molecular weight poly(arylenesulfide ketone)s are prepared by contacting in a reaction mixture,preferably in a polar solvent, a polyhalobenzophenone and an alkalimetal hydrosulfide present in a small but important closely definedamount over the stoichiometric amount of alkali metal sulfide needed inthe condensation polymerization.

In a first embodiment, presently preferred, the alkali metal sulfide isprepared by bringing together an alkali metal hydrosulfide with analkali metal hydroxide at a molar ratio of about 1.004:1 to about1.038:1 so as to have the defined slight excess of alkali metalhydrosulfide.

In a further embodiment, I have discovered that high molecular weightpoly(arylene sulfide ketone)s are prepared by contacting in a reactionmixture a polyhalobenzophenone, an alkali metal sulfide and an alkalimetal hydrosulfide, preferably in a polar solvent, wherein an alkalimetal .[.sulfide.]. .Iadd.hydrosulfide .Iaddend.is brought together withan alkali metal .[.hydrosulfide.]. .Iadd.sulfide .Iaddend.at a molar.[.ration.]. .Iadd.ratio .Iaddend.of about .[.1.004:1.]. .Iadd.0.004:1.Iaddend.to about .[.1.038:1.]. .Iadd.0.038:1 .Iaddend.underpolymerization conditions effective for producing the poly(arylenesulfide ketone), again so as to have the defined slight excess of alkalimetal hydrosulfide.

In either embodiment, or combination thereof, desired is about 0.004 toabout 0.038 molar excess of alkali metal hydrosulfide relative to thepolyhalobenzophenone, that is in addition to the alkali metal sulfideadded or formed in situ.

Poly(arylene sulfide ketone)s having an inherent viscosity of at leastabout 0.48 are obtained by my processes for producing the poly(arylenesulfide ketone)s. This is unexpected in my experience when consideringhow important stoichiometry is for condensation polymerizations.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical representation of the inherent viscosity ofpoly(phenylene sulfide ketone)s prepared in the condensationpolymerization reaction employing a slight amount of sodium bisulfide(sodium hydrosulfide (NaSH) in a reaction mixture containing4,4'dichlorobenzophenone, sodium sulfide (Na₂ S), andN-methyl-2-pyrrolidone (NMP). The graph indicates by the portion betweenthe larger dashed lines that poly(phenylene sulfide ketone)s having aninherent viscosity of at least about 0.55 are obtained when a slightmolar excess of NaSH of about 1 to about 3.5 mole percent over thatneeded to form Na₂ S was employed in the reactionmixture. The graphindicates by the portion between the shorter dashed lines thatpoly(phenylene sulfide ketone)s having an inherent viscosity of at leastabout 0.65 are obtained when a molar excess of NaSH of about 1.5 toabout 3.3 mole percent was employed in the reaction mixture.

These results are in sharp contrast to poly(phenylene sulfide ketone)shaving an inherent viscosity of less than about 0.45 prepared employingan alkali metal bisulfide with an alkali metal hydroxide at astoichiometric molar ratio of about 1:1, thus no excess NaSH, and at ahigher ratio of about 1.05:1. Only the narrow ratio was effective.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with my invention, poly(arylene sulfide ketone)s areprepared by contacting in a reaction mixture (a) at least onepolyhalobenzophenone, (b) at least one alkali metal sulfide either addedas such or the equivalent in situ from an alkali metal hydrosulfide andan alkali metal hydroxide or both, and (c) alkali metal hydrosulfide,preferably in a polar solvent.

In one embodiment, the alkali metal sulfide employed in the process ofmy invention can be prepared from an alkali metal hydrosulfide and analkali metal hydroxide in an aqueous solution using defined ratios. In afurther embodiment, the alkali metal sulfide can be employed with thealkali metal hydrosulfide in an aqueous solution. In either embodimentthe amount of the hydrosulfide is critical to the production ofpoly(arylene sulfide ketone)s of high inherent viscosity.

In the first embodiemnt, the reaction of a dihalobenzophenone, such as4,4' dichlorobenzophenone, with an alkali metal sulfide, prepared froman alkali metal hydrosulfide and an alkali metal hydroxide, such assodium hydrosulfide and sodium hydroxide, in a polar solvent, such asN-methyl-2-pyrrolidone (NMP), so as to form a poly(phenylene sulfideketone) of repeating units of poly(phenylene sulfide ketone), can berepresented by: ##STR1##

In the further embodiment, the polymerization employs adihalobenzophenone, such as 4,4' dichlorobenzophenone, with an alkalimetal sulfide, such as sodium sulfide, and an alkali metal hydrosulfide,such as sodium hydrosulfide, in a polar solvent, such as NMP, to form apoly(phenylene sulfide ketone) of repeating units of poly(phenylenesulfide ketone), can be represented by: ##STR2##

In my invention, a slight but essential molar excess of alkali metalhydrosulfide is employed with respect to the dihalobenzophenone or akalimetal sulfide.

Although the molar excess of alkali metal hydrosulfide to alkali metalhydroxide can vary somewhat, generally when alkali metal hydrosulfide isemployed with alkali metal hydroxide, it will be within the range ofabout 0.4 to about 3.8 mole percent, preferably within the range ofabout 1 to about 3.5 mole percent over the stoichiometric amountcalculated to form alkali metal sulfide. The corresponding molar ratioof alkali metal hydrosulfide to alkali metal hydroxide will be in therange of about 1.004:1 to about 1.038:1, preferably within the range ofabout 1.01:1 to about 1.035:1.

In a further embodiment of my invention, an alkali metal hydrosulfideand an alkali metal sulfide are employed in a range of about 0.4 to.[.aobut.]. .Iadd.about .Iaddend.3.8 mole percent, preferably within therange of about 1 to about 3.5 mole percent, relative to the alkali metalsulfide amount as 100, again to assure a slight but essential excess ofalkali metal hydrosulfide. The corresponding molar ratio of alkali metalhydrosulfide to alkali metal sulfide is in the range of about.[.1.004:1.]. .Iadd.0.004:1 .Iaddend.to about .[.1.038:1.]..Iadd.0.038:1.Iaddend., preferably .[.int he.]. .Iadd.in the.Iaddend.range of about .[.1.01:1.]. .Iadd.0.01:1 .Iaddend.to about.[.1.035:1.]. .Iadd.0.035:1.Iaddend..

The poly(arylene sulfide ketone)s prepared according to my processeswill have an inherent viscosity of at least about 0.48, preferably fromabout 0.55 to about 0.77. The polymers have wide utility for film,fiber, moldings, and composite applications because of this high meltingpoint and high molecular weight.

FIG. 1 is a graphical representation of the inherent viscosity ofpoly(phenylene sulfide ketone)s as representative of poly(arylenesulfide ketone)s prepared from the condensation reaction of a molarexcess of NaSH with respect to NaOH of about 0 to about 5 moles percentin a polymerization mixture containing 4,4'dichlorobenzophenone and NMP.The graph indicates by the portion between the longer dashed line thatpoly(phenylene sulfide ketone)s having an inherent viscosity of at leastabout 0.55 are obtained when a molar excess of NaSH fo about 1 to about3.5 mole percent was employed. The shorter dashed lines indicate thatpoly(phenylene sulfide ketone)s having an inherent viscosity of at leastabout 0.65 are obtained when a molar excess of NaSH versus NaOH of about1.1 to 3.3 mole percent was employed. This is in sharp contrast to thepoly(arylene sulfide ketone)s having an inherent viscosity of less thanabout 0.45 obtained by bringing together a dihalobenzophenone, an alkalimetal bisulfide, and an alkali metal hydroxide at a stoichiometric molarratio of about 1:1:1 and at a higher ratio of about 1:1.05:1.

My process employs a polyhalobenzophenone, preferably adihalobenzophenone. The dihalobenzophenones can be represented by theformula: ##STR3## wherein each X is selected from the group consistingof chlorine, bromine, fluorine, and iodine. Among thepolyhalobenzophenones which can be employed are4,4'dichlorobenzophenone, 4,4'difluorobenzophenone,4,4'dibromobenzophenone, 4,4'diiodobenzophenone,2,4'dichlorobenzophenone, 2,4,4'trichlorobenzophenone,2,4,4'triiodobenzophenone, 2,4,4'trifluorobenzophenone,2,4,4'tribromobenzophenone, and the like, and mixtures thereof. Thepresently preferred dihalobenzophenone, due to its effectiveness andcommercial availability, is 4,4'dichlorobenzophenone.

The alkali metal sulfides include lithium sulfide, sodium sulfide,potassium sulfide, rubidium sulfide, cesium sulfide, and mixturesthereof. The alkali metal hydrosulfides (sometimes called bisulfides)include lithium hydrosulfide, sodium hydrosulfide, potassiumhydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixturesthereof. The alkali metal hydroxides include lithium hydroxide, sodiumhydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide,and mixtures thereof.

The preferred alkali metal sulfide, due to its effectiveness, is sodiumsulfide (Na₂ S). The preferred alkali metal hydrosulfide, due to itseffectiveness, is sodium hydrogen sulfide (NaSH). The preferred alkalimetal hydroxide, due to its effectiveness, is sodium hydroxide (NaOH).

The molar ratio of dihalobenzophenone: alkali metal sulfide should beheld as close to stoichiometric ratio of 1:1 as possible in thecondensation polymerization.

The solvents useful in the process of my invention are polar organicsolvents which can be used with a dihalobenzophenone and an alkali metalsulfide in the production of poly(arylene sulfide ketone)s. These polarorganic solvents include such as the amides and sulfones. Specificexamples of such polar organic solvents include hexamethylphosphoramide, tetramethylurea, N,N'-ethylenedipyrrolidone,N-methyl-2-pyrrolidone (NMP), pyrrolidone, caprolactam,N-ethylcaprolactam, sulfolane, N,N'-dimethylacetamide, diphenyl sulfone,and the like, and mixtures thereof. The preferred polar organic solvent,due to its effectiveness and commercial availability, is NMP. The amountof solvent can vary, as is known in the art.

The order of addition of the ingredients used to prepare thepoly(arylene sulfide ketone)s can be varied as desired. Generally, thealkali metal sulfide (such as Na₂ S), and the alkali metal hydrosulfide(such as NaSH), or the alkali metal hydroxide (such as NaOH) and thealkali metal hydrosulfide (such as NaSH), and the dihalobenzophenone,(such as 4,4' dichlorobenzophenone), can be added to a reactor vessel inany order. The polar organic solvent, (such as NMP), will generally beadded to the reaction mixture following the addition of theaforementioned ingredients.

Although the reaction temperature at which the polymerization sisconducted can vary over a wide range, generally it will be within therange of about 125° C. to about 450° C., preferably about 175° C. toabout 350° C., most preferably about 225° C. to about 275° C. Thereaction time can vary widely, depending in part on the reactiontemperature, but generally will be within the range of about 10 minutesto about 72 hours, preferably about 1 hour to about 20 hours. Thepressure should be sufficient to maintain the the reaction mixturesubstantially in the liquid phase. The pressure will generally be withinthe range of about 0 psig to about 300 psig, preferably 150 to about 250psig.

The polymer can be recovered as desired, preferably by removing thepolymer and solvent from a cooled reactor and recovering the polymer byfiltration. The polymer can be subsequently washed with water and driedin a vacuum oven.

EXAMPLES

Examples provided are intended to assist in a further understanding ofmy invention. Particular materials employed, species, conditions, areintended to be further illustrative of my invention and not limitativeof the reasonable scope thereof.

EXAMPLE I

In this example the preparation of a poly(phenylene sulfide ketone)(PPSK) resin with equimolar amounts of NaSH and NaOH is described. To a1-liter stainless steel reactor fitted with a double helical stirrer,nitrogen inlet tube, and rupture disc were charged: 41.63 grams ofsodium hydrogen sulfide flakes (containing 58.17 weight-% NaSH, 0.35weight-% Na₂ S, and about 41.4 weight-% H₂ O), 17.58 grams of sodiumhydroxide pellets (98.2 weight-% NaOH, provided by Mallinckrodt, Inc.,St. Louis, Mo.), 108.48 grams of 4,4'-dichlorobenzophenone (DCBP,provided by Aldrich Chemical Company, Milwaukee, Wisc.), and 343 grams(3.46 moles) of N-methyl-2-pyrrolidione (NMP). Thus an equal number ofmoles (0.432) of each of NaSH, NaOH, and DCBP were charged, and themolar H₂ O: NaSH ratio was about 2.2:1.

The reactor was sealed, alternately pressured with 100 psig N₂ and thenvented so as to remove air. The reactor mixture was then stirred andheated to about 250° C. (during a one hour period). This temperature wasmaintained for about 3 hours, while a pressure of about 180 psig wasestablished. The reactor was then cooled to about 200° C., and 3 gramsof DCBP plus 100 grams of NMP were charged for end-capping the formedPPSK polymer with DCBP. The reactor contents were again heated to about250° C. and kept at that temperature for about 1 hour.

The polymer of thi run (Run 1) was removed from the cooled reactor,recovered by filtration through a Buchner funnel, washed seven timeswith 2.5 liter aliquots of hot deionized water (about 70° C.), and driedin a vacuum oven at about 80° C. The inherent viscosity (IV) of the PPSKpolymer measured at 30° C. in a #200 viscometer using a 0.5 weight-%solution in concentrated H₂ SO₄ as solvent, was 0.45. Polymer yield was73.6 grams.

In a second run (Run 2), an equimolar mixture of NaSH, NaOH, and DCBP inNMP was polymerized at essentially the same process conditions asdescribed above, except that the mixture of NaSH, NaOH, H₂ O, and NMPwas first allowed to dehydrate at 0 psig and 160°-250° C. before allDCBP was added to the cooled reactor (about 105°), and no end-cappingwith DCBP was carried out. Then the reactor was sealed and heated at250° C./130 psig for 3 hours. The inherent viscosity of the washed anddried PPSK polymer was 0.28.

Runs 3-8 reflect the preparation of PPSK employing increased molarratios of NaSH relative to NaOH, otherwise essentially in accordancewith the procedure of Run 1 (no dehydration; polymerization of 250° C.for 3 hours; end-capping with DCBP at 250° C. for 1 hour; molar H₂ O:NaSH ratio of about 2.2:1).

Results are summarized in Table I:

                  TABLE I                                                         ______________________________________                                                             Molar   Molar Ratio                                                                             (IV)                                        Moles   Moles   Excess  of        Inherent                               Run  NaSH    NaOH    of NaSH NaSH to NaOH                                                                            Viscosity                              ______________________________________                                        1    0.432   0.432   0          1:1    0.45                                   2    0.500   0.500   0          1:1    0.28                                   3    0.434   0.432   0.5%    1.005:1   0.49                                   4    0.432   0.426   1.4%    1.014:1   0.64                                   5    0.441   0.432   2.0%    1.020:1   0.73                                   6    0.443   0.432   2.5%    1.025:1   0.68                                   7    0.445   0.432   3.0%    1.030:1   0.77                                   8    0.449   0.432   4.0%    1.039:1   0.45                                   9    0.454   0.432   5.1%    1.051:1   0.33                                   ______________________________________                                    

Runs 3-8 demonstrate that when a small defined molar excess of alkalimetal hydrosulfide is used, the IV of the resultant polymer product willbe equal to or greater than the IV of polymer products resulting fromthe use of a stoichiometric amount of alkali metal hydrosulfide NaSH(Runs 1 or 2) or the use of a larger excess (Run 9) of alkali metalhydrosulfide. The data, plotted in FIG. 1, show that PPSK polymershaving an inherent viscosity of at least about 0.45 were obtained when amolar excess of NaSH (versus NaOH) of about 0.4% to about 3.8% wasemployed in the reaction mixture.

Thermal transitions were measured for the PPSK resin produced in Run 5employing a Perkin-Elmer DAC-2C differential scanning calorimeterequipped with a computerized data system and a Perkin-Elmer TADS-1plotter. The polymer sample was heated at a rate of 20° C./minute.

Results obtained were: glass transition temperature Tg=144° C.;crystallization temperature Tc=191° C.; melting temperature Tm=340° C.;melt crystallization temperature (upon cooling of the melt) Tmc=291° C.

EXAMPLE II

In this example, the preparation of PPSK, essentially in accordance withthe procedure of Run 1 (Example I), employing Na₂ S flakes (rather thanNaSH and NaOH) is described. 56.88 grams of sodium sulfide flakes(containing about 59.3 weight-% Na₂ S, about 1.3 weight-% NaSH, andabout 39.4 weight-% H₂ O, equal to 0.432 moles of Na₂ S.[.),plus.]..Iadd., .Iaddend.0.013 moles of NaSH and 1.25 moles ofwater.Iadd.).Iaddend., were reacted with 0.432 moles of DCBP in thepresence of 3.46 moles of NMP.

The presence of NaSH was equivalent to a molar NaSH excess of about 3%.The IV of the formed PPSK resin (about 89 grams yield) was 0.58.Therefore, the use of an alkai metal sulfide such as Na₂ S, plus adefined slight excess of alkali metal hydrosulfide, such as NaSH,clearly is effective and within the scope of this invention.

EXAMPLE III

This example illustrates the curing of PPSK so as to further increaseits molecular weight. The dark-colored resin prepared in Run 6 wasplaced in an air oven heated to 316° C. The inherent viscosity of thepolymer increased from an initial value of 0.68 to 0.84 after 30minutes, and to 0.97 after 60 minutes. After heating for about 120minutes, the polymer was no longer soluble in H₂ SO₄. Degassing of thepolymer during curing, especially during the first hour, was observed.

I claim:
 1. A method for preparing a poly(arylene sulfide ketone) comprising:contacting in a reaction mixture (a) at least one polyhalobenzophenone, employing about .[.1.004:1 to about 1.038:1 molar ratios.]. .Iadd.0.004 to about 0.038 molar excess .Iaddend.of alkali metal hydrosulfide relative to said polyhalobenzophenone, and at least one of (b) or (c), wherein (b) is at least one alkali metal sulfide and at least one alkali metal hydrosulfide, and (c) is at least one alkali metal hydroxide and at least one alkali metal hydrosulfide, under polymerization conditions effective for producing the poly(arylene sulfide ketone);
 2. The method of claim 1, wherein the polyhalobenzophenone comprises a dihalobenzophenone, and the reaction mixture includes a polar reaction medium.
 3. The method of claim 2, employing .[.the.]. .Iadd.about 0.01 to about 0.035 molar excess of said .Iaddend.alkali metal hydrosulfide .[.in a ratio of about 1.01:1 to about 1.035:1.]. relative to said polyhalobenzophenone, .Iadd.and said .Iaddend.alkali metal hydroxide .[.and.]. .Iadd.or said .Iaddend.alkali metal sulfide.
 4. The method of claim 2, wherein the alkali metal hydrosulfide comprises sodium hydrosulfide, the alkali metal hydroxide comrpises sodium hydroxide, the dihalobenzophenone comprises 4,4'dichlorobenzophenone, and the polar reaction medium comprises N-methyl-2-pyrrolidone.
 5. The method of claim 4, wherein the poly(arylene sulfide ketone) is represented by repeating units of the structural formula: ##STR4##
 6. The method of claim 1, wherein the poly(arylene sulfide ketone) comprises poly(phenylene sulfide ketone).
 7. The method of claim 6, employing said (c), wherein said alkali hydrosulfide is sodium hydrosulfide, and said alkali metal hydroxide is sodium hydroxide.
 8. The method of claim 6, wherein the poly(phenylene sulfide ketone) exhibits an inherent viscosity of at least about 0.48 measured at 30° C. in a #200 viscometer using an 0.5 weight percent solution in concentrated H₂ SO₄.
 9. The method of claim 8, wherein the poly(phenylene sulfide ketone) exhibit an inherent viscosity of about 0.55 to about 0.77.
 10. The method of claim 1, wherein the polymerization conditions include a temperature of about 175° C. to about 350° C., a pressure of about 0 psig to about 200 psig, and a reaction time of about 1 hour to about 72 hours.
 11. The method of claim 1, employing said (b), wherein the alkali metal hydrosulfide is present in a .[.stoichiometric.]. .Iadd.molar .Iaddend.excess of about .[.1.004:1 to about 1.038:1.]. .Iadd.0.004 to about 0.038 .Iaddend.over the alkali metal sulfide.
 12. The method of claim 11, wherein the alkali metal .[.sulfide.]. .Iadd.hydrosulfide .Iaddend.is brought together with the akali metal .[.hydrosulfide at.]. .Iadd.sulfide in .Iaddend.a molar .[.ratio.]. .Iadd.excess .Iaddend.of about .[.1.01:1 to about 1.035:1.]. .Iadd.0.01 to about 0.035.Iaddend.. 